Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
  • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/916—Dicarboxylic acids and dihydroxy compounds

Definitions

• the instant invention is directed to a process for making polyesters.
• the process employs epoxides or episulfides which unexpectedly result in improved polymerization of molten macrocyclic polyester oligomers.
• Polyesters such as poly(alkylene terephthalates) are well known commercially available polymers. They have valuable characteristics including strength, toughness, high gloss and solvent resistance. Polyesters are commercially prepared by the reaction of diols with functional derivatives of dicarboxylic acids, diacid halides or esters. Further, the above-described polyesters may be fabricated into articles by a number of well known techniques including injection and roto molding and extrusion.
• polyesters are prepared by contacting macrocyclic polyester oligomers and a polymerization catalyst at a temperature within the range of about 160-300°C.
• the instant invention is directed to a process for making polyesters comprising the step of contacting in the presence of at least one compound selected from the group consisting of epoxides and episulfides:
• the oligomers may be prepared by a method which comprises contacting at least one diol of the formula HO-R-OH and at least one diacid chloride of the formula under substantially anhydrous conditions and in the presence of a substantially water immiscible organic solvent, with at least one unhindered tertiary amine; said contact being conducted at a temperature from about -25° to about +25°C.
• reagents used to synthesize the macrocyclic poly(alkylene dicarboxylate) oligomers employed in the instant invention include unhindered tertiary amines and substantially water-immiscible organic solvents.
• a detailed description for the preparation of the above-mentioned macrocyclic polyester oligomers employed in this invention may be found in commonly assigned U.S. Patent 5,039,783, the disclosure of which is incorporated herein by reference.
• catalysts which may be employed in this invention are those which are capable of enhancing the polymerization of the macrocyclic polyester oligomers described above.
• the often employed catalysts include organotin compounds and titanate catalysts.
• organotin compounds are dialkyltin(IV) oxides such as di-n-butyltin(IV) oxide and di-n-octyltin oxide and acyclic and cyclic dialkyltin(IV) dialkoxides such as di-n-butyltin(IV) di-n-butoxide and 2,2-di-n-butyl-2-stanna-1,3-dioxacycloheptane tributyltin ethoxide.
• Illustrative titanate catalysts include isopropyl titanate, 2-ethylhexyl titanate, and tetrakis-(2-ethylhexyl)titanate.
• epoxides which may be employed in this invention include aliphatic diepoxides such as dodecatriene dioxide, dipentene dioxide and 1,2,7,8-diepoxyoctane; bis-glycidyl ethers/esters such as the bisglycidyl ether of bisphenol A and its condensation products; alicyclic diepoxides such as 3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate and bis(3,4-epoxycyclohexylmethyl) adipate; mixed aliphatic/alicyclic diepoxides such as vinylcyclobutene dioxide, vinylcyclopentadiene dioxide and butenylcyclopentene dioxide; glycidyl ethers of novolak resins; epoxidized heterocycles such as triglycidyl isocyanurate; and epoxidized oils such as epoxidized tall oil, linseed oil and soybean
• Still other epoxides which may be employed in this invention include, for example, alicyclic epoxides which may be hindered, less-hindered or unhindered as defined in The Determination of Epoxide Groups , B. Dobinson et al, Pergamon Press, 1969.
• thio analogs of the epoxides described above wherein thio analog is defined herein to mean the oxygen of the epoxide is replaced with sulfur.
• epoxidation co-catalysts like tetrabutylphosphonium bromide in this invention.
• the preferred epoxides and episulfides employed in this invention often have the formula A-B-A , wherein each A is independently and each R is independently a hydrogen, halogen, hydroxy group, alkoxy group, C 1-10 hydrocarbon or substituted or unsubstituted aromatic radical and Z is oxygen or sulfur.
• B is a divalent bridging radical or group, wherein the divalent bridging radical is not limited and often a substituted or unsubstituted -C- or alicyclic or aromatic radical and the bridging group is not limited and often a substituted or unsubstituted polycyclic, polyaromatic or aliphatic group.
• Said bridging group may also be a member having the formulae wherein R is as previously defined and each q is independently about 0 to about 30 and often 0 or 1.
• the often preferred epoxide employed in this invention is commercially available and is 3,4-epoxycyclohexyl 3,4-epoxycyclohexylcarboxylate.
• a reaction vessel When conducting the instant novel method, a reaction vessel may be charged with the macrocyclic polyester oligomers, polymerization catalysts and epoxide and/or episulfide and their order of addition is not material. Heat is supplied to melt the oligomers (about 135°C to about 250°C) for polymerization and stirring may be employed under an inert gas in order to enhance the polymerization of the oligomers to produce the desired polymer. Additionally, the epoxides and polymerization catalysts employed in this invention may first be dissolved in a solvent such as o-dichlorobenzene in order to enhance mixing.
• a solvent such as o-dichlorobenzene
• the desired polyesters produced in this invention often include poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(1,2-ethylene 2,6-naphthalene dicarboxylate) and copolyesters comprising the same.
• the resulting mixture was stirred for about 5 minutes after which 69 ⁇ L of a 1 M solution of tetrakis-(2-ethylhexyl)titanate and 0-dichlorobenzene (0.30 mole % titanate) were added.
• the mixtrure with titanate was stirred and crystalline polymer formed within 10 seconds.
• the flask was removed from the oil bath and was broken to retrieve a sample of polymer.
• the polymer was dissolved in a solution of 15% hexafluoroisopropanol and 85% chloroform. GPC analysis of the resulting solution unexpectedly showed 96.4% polymerization.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polyesters Or Polycarbonates (AREA)

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Publications (3)

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• 1995
  • 1995-06-19 US US08/497,694 patent/US5498651A/en not_active Expired - Lifetime
• 1996
  • 1996-04-04 EP EP96302451A patent/EP0749999B1/de not_active Expired - Lifetime
  • 1996-04-04 ES ES96302451T patent/ES2153937T3/es not_active Expired - Lifetime
  • 1996-04-04 DE DE69611269T patent/DE69611269T2/de not_active Expired - Fee Related
  • 1996-04-15 JP JP09162096A patent/JP3510952B2/ja not_active Expired - Fee Related

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